Saccharin-5-carbonyl derivatives with herbicidal effect

ABSTRACT

The present application relates to saccharin-5-carbonyl derivatives of the formula I                    
     in which the substituents have the following meanings: 
     L is C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy; 
     Z is C 1 -C 6 -alkyl, C 3 -C 8 -cycloalkyl, C 3 -C 6 -alkenyl, C 3 -C 5 -alkynyl, phenyl-C 1 -C 6 -alkyl or phenyl, where the phenyl rings are in each case optionally mono- or polysubstituted by C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy or halogen; 
     M is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, halogen, cyano, nitro or halo-C 1 -C 6 -alkyl; 
     R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8  are hydrogen, C 1 -C 6 -alkyl; 
     and agriculturally utilizable salts of the compound I.

This application is a 371 of PCT/EP00/01408 filed Feb. 21, 2000.

The present application relates to saccharin-5-carbonyl derivatives ofthe formula I

in which the substituents have the following meanings:

L is C₁-C₆-alkyl, C₁-C₆-alkoxy;

Z is C₁-C₆-alkyl, C₃-C₈-cycloalkyl, C₃-C₆-alkenyl, C₃-C₅-alkynyl,phenyl-C₁-C₆-alkyl or phenyl, where the phenyl rings can be mono- orpolysubstituted by C₁-C₆-alkyl, C₁-C₆-alkoxy and halogen;

M is hydrogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, halogen, cyano, nitro orhalo-C₁-C₆-alkyl;

R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ are hydrogen, C₁-C₆-alkyl;

or the agriculturally utilizable salts of the compound I.

The invention further relates to crop protection compositions comprisingthe compounds I and processes for controlling undesired vegetation withthe saccharin derivatives I and use of the compounds I for theproduction of crop protection compositions having herbicidal action.

WO 96/05182, WO 98/40366 and U.S. Pat. No. 5,801,120 discloseherbicidally active saccharincarbonylcyclohexanedione derivatives.

EP-A 338 992 describes herbicidal benzoyl derivatives which do not havea saccharin structure.

The use of saccharin derivatives as fungicides is furthermore known,e.g. JP Publication 72/00419 and 73/35457 and in pharmacy, e.g. EP-A 594257.

The herbicidal properties of the known compounds and the compatibilitywith crop plants are, however, only of limited satisfactoriness.

The object of the present invention is to make available alternativesaccharin derivatives having novel structural features. Surprisingly, ithas been found that the saccharin derivatives of the formula I haveimproved properties in comparison with the saccharin derivatives knownhitherto.

Compounds of the formula I are obtained according to Scheme 1 byacylating diones of the formula II with a saccharin-5-carbonyl chlorideof the formula III and rearranging the enol esters of the formula IVobtained in the presence of a catalyst to give the active compound ofthe formula I.

In the above Scheme 1, the substituents R¹ to R⁸, L, M and Z have themeaning given at the outset. X is an easily removable group, such as,for example, halogen, in particular chlorine, or an anhydride groupderived from an organic or inorganic acid.

The first step of the reaction sequence in Scheme 1 is carried out byaddition of the acid halide III to the solution or suspension of thedione II in the presence of an auxiliary base. The reactants and theauxiliary base are Preferably employed in equimolar amounts, but a smallexcess of 1.2 to 1.5 molar equivalents of the auxiliary base can beadvantageous. Solvents which can be used are methylene chloride,tetrahydrofuran, ethyl acetate, toluene or preferably acetonitrile.Suitable auxiliary bases are alkali metal carbonates, pyridine ortertiary alkylamines, preferably triethylamine. During the addition ofthe acid chloride, the reaction mixture is preferably cooled to 0 to 10°C., and then it is stirred at a temperature of 20 to 70° C., inparticular 25 to 40° C., until the reaction is complete.

The enol ester IV can be isolated before the rearrangement, but thereaction is preferably carried out by adding two to four, preferably2.5, equivalents of triethylamine to the reaction mixture and thenadding 2 to 10, in particular 3, mol % of a cyano compound such asacetone cyanohydrin or preferably trimethylsilyl cyanide at 25° C. andthen stirring at a temperature of 20 to 40° C., preferably at 25° C.,until the enol ester IV is no longer present. Examples of thecyanide-catalyzed rearrangement of enol esters are found in EP 338 992and EP 0 252 298.

Working-up is carried out by acidifying the reaction mixture with 5%strength by weight hydrochloric acid or sulfuric acid and thenextracting with a solvent such as ethyl acetate or methylene chloride.After drying the extract over sodium sulfate or magnesium sulfate, thesolvent is distilled off in vacuo and the crude product is subjected, ifnecessary, to purification. For purification, the reaction product canbe, for example, chromatographed (silica gel, cyclohexane/ethyl acetate)or recrystallized (methanol/water or glacial acetic acid/water). Afurther purification method is extraction of an ethyl acetate solutionof the crude product with an aqueous alkali metal carbonate solution,the final product passing into the aqueous phase. Acidification of theaqueous solution and fresh extraction yields the final product, afterdrying and removing the solvent, in purer form.

The diones of the formula II used as starting materials are known andcan be prepared in a manner known per se [cf. EP-A 338 992; R. Gleiter,Tetrahedron 1980, 36: 655; JP 10,265441; JP 10, 265415].

The acid halides of the formula III used as starting materials arelikewise known. If X=Cl, they are obtained by reaction of a suitablysubstituted saccharin-5-carboxylic acid with thionyl chloride. Thesynthesis of substituted saccharin-5-carboxylic acids is described, forexample, in DE 44 27 996.

In the definition of the various radicals in formula I, the termsindicated are, either per se (such as, for example, C₁-C₆-“alkyl”) or asmoieties or in combination with chemical groups of different composition(such as, for example, C₁-C₆-halo-“alkyl”, phenyl-C₁-C₆-“alkyl”),fundamentally a collective term for a group of compounds. In the case inwhich the phenyl rings can be mono- or polysubstituted, the substituentscan fundamentally be identical or different.

In the definitions of the compounds I given at the beginning, collectiveterms were used which are generally representative of the followinggroups:

alkyl: straight-chain or branched alkyl groups having 1 to 6, preferably1-4, carbon atoms, e.g. C₁-C₄-alkyl such as methyl, ethyl, propyl,1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and1,1-dimethylethyl;

alkoxy: straight-chain or branched alkyl groups having 1 to 6,preferably 1-4, carbon atoms as mentioned above, which are bonded to thestructure via an oxygen atom (—O—), e.g. C₁-C₃-alkoxy such as methyloxy,ethyloxy, propyloxy and 1-methylethyloxy;

cycloalkyl: monocyclic alkyl groups having 3 to 8 carbon ring members,e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl andcyclooctyl;

alkenyl: straight-chain or branched alkenyl groups having 2, preferably3 to 6, carbon atoms and a double bond in any desired position, e.g.C₂-C₆-alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl,1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl,2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl,1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl,2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl,2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl,2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl,1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl,1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl,5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl,3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl,2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl,1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl,4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl,3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl,1,1-dimethyl-3-butenyl, 2,1-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl,1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl,1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl,2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl,3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl,1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl,2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl,1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and1-ethyl-2-methyl-2-propenyl,

alkynyl: straight-chain or branched alkynyl groups having 3 to 5 carbonatoms and a triple bond in any desired position, e.g. C₃-C₅-alkynyl suchas 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-pentynyl,3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl,2-methyl-3-butynyl, 1,1-dimethyl-2-propynyl and 1-ethyl-2-propynyl;

halogen: fluorine, chlorine, bromine and iodine; preferably fluorine orchlorine;

haloalkyl: a C₁-C₆-alkyl radical as mentioned above, which is partiallyor completely substituted by fluorine, chlorine, bromine and/or iodine,e.g. trichloromethyl, trifluoromethyl, difluoromethyl, 2-fluoroethyl,2-chloroethyl, 2-bromoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl,2,2,2-trichloroethyl, 2-fluoropropyl, 3-fluoropropyl, 2-chloropropyl or3-chloropropyl, in particular trifluoromethyl;

phenylalkyl: a C₁-C₆-alkyl radical as mentioned above, which issubstituted by phenyl in any desired position, in particular benzyl,2-phenylethyl.

Phenyl rings may, in principle, be unsubstituted or substituted.Substituted phenyl rings are preferably mono-, di- or trisubstituted byalkyl, alkoxy or halogen. The substituents may be in the 2-, 3- or4-position. In the case of monosubstituted phenyl rings, preference isgiven to the 2- or 4-position, and, in the case of disubstituted phenylrings, preference is given to the 2,4-position.

With respect to the intended use as herbicides, saccharin-5-carbonylderivatives of the formula I are preferred where the following radicalsper se or in combination with one another have the following meanings inparticular:

1. L: C₁-C₃-alkyl, such as, for example, methyl, ethyl; C₁-C₃-alkoxy,such as, for example, methoxy, ethoxy; in particular methyl.

2. Z: C₁-C₄-alkyl, C₃-C₈-cycloalkyl, C₃-C₆-alkenyl, C₃-C₅-alkynyl,benzyl and phenyl.

3. Z as under item 2, in particular methyl, ethyl, i-propyl, i-butyl,t-butyl, cyclopropyl; cyclohexyl, allyl, propargyl, phenyl and benzyl;particularly preferably methyl, ethyl and phenyl and very particularlypreferably methyl.

4. M: hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, fluoro, chloro, cyano, nitro,halo-C₁-C₄-alkyl.

5. M as under item 4, in particular methyl, ethyl, methoxy, ethoxy,fluoro, chloro, cyano, nitro and trifluoromethyl.

6. M as under item 4 or 5, preferably hydrogen, methyl, ethyl, methoxyand chlorine; particularly preferably hydrogen, methyl and chlorine.

7. R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ : hydrogen, C₁-C₃-alkyl. Preferably,5-8 of the radicals R¹-R⁸ are hydrogen and up to three radicals arealkyl, in particular methyl.

8. R⁷ and R⁸ are preferably identical and are in particular hydrogen ormethyl.

Preferred compounds are also those of the formulae I, II, III and IVwhich result from single or multiple combinations of the meaningsmentioned under items 1.-8.

Very particularly preferred saccharin derivatives of the formula I arethose in which the substituents contain one or more of the followingfeatures:

1. L: methyl.

2. R¹-R⁸: in each case hydrogen.

3. Z: methyl.

4. M: hydrogen, methyl or chlorine.

The compounds I can be present in the form of their agriculturallyutilizable salts, where the nature of the salts in general does notmatter. Customarily, the salts of those bases will be suitable which donot adversely affect the herbicidal action of I.

Suitable basic salts are particularly those of the alkali metals,preferably the lithium, sodium and potassium salts, those of thealkaline earth metals, preferably calcium, magnesium and barium saltsand those of the transition metals, preferably manganese, copper, zincand iron salts, ammonium salts, and also ammonium salts which can carryone to four C₁-C₄-alkyl, or hydroxy-C₁-C₄-alkyl substituents, a phenylor benzyl substituent, preferably diethylammonium, diisopropylammonium,tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, andtrimethyl(2-hydroxyethyl)ammonium salts, the phosphonium salts, thesulfonium salts, preferably tri-(C₁-C₄)alkyl sulfonium salts, and thesulfoxonium salts, preferably tri-(C₁-C₄)alkylsulfoxonium salts.

The compounds I and their agriculturally utilizable salts aresuitable—both as isomer mixtures and in the form of the pure isomers—asherbicides. The herbicidal compositions comprising I control vegetationon uncultivated areas very well, particularly at high application rates.In crops such as wheat, rice, corn, soybeans and cotton, they actagainst broad-leaved weeds and grass weeds without noticeably damagingthe crop plants. This effect occurs especially at low application rates.

Depending on the particular application method, the compounds I orcompositions comprising them can additionally be employed in a furthernumber of crop plants for eliminating undesired plants. Suitable cropsare, for example, the following:

Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis,Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napusvar. napus, Brassica napus var. napobrassica, Brassica rapa var.silvestris, Camellia sinensis, Carthamus tinctorius, Caryaillinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffeacanephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucuscarota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypiumhirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypiumvitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare,Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linumusitatissimum, Lycopersicon lycopersicum, Malus spec., Manihotesculenta, Medicago sativa, Musa spec., Nicotiana tabacum (N.rustica),Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris,Picea abies, Pinus spec., Pisum sativum, Prunus avium, Prunus persica,Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharumofficinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (S.vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum,Triticum durum, Vicia faba, Vitis vinifera, Zea mays.

Moreover, the compounds I can also be used in crops which have been madetolerant to the action of herbicides by means of breeding, includinggenetic engineering methods.

The herbicidal compositions or the active compounds can be appliedpreemergence or postemergence. If the active compounds are lesstolerable to certain crop plants, application techniques can be used inwhich the herbicidal compositions are sprayed with the aid of the sprayequipment such that the leaves of the sensitive crop plants are notaffected if possible, while the active compounds reach the leaves ofundesired plants growing under them or the uncovered soil surface(post-directed, lay-by).

The compounds I and the herbicidal compositions comprising them can beapplied by spraying, atomizing, dusting, broadcasting or watering, forexample in the form of directly sprayable aqueous solutions, powders,suspensions, also high-percentage aqueous, oily or other suspensions ordispersions, emulsions, oil dispersions, pastes, dusting agents,broadcasting agents or granules. The application forms depend on theintended use; if possible they should in each case guarantee the finestdistribution of the active compounds according to the invention.

Suitable inert additives are mainly: mineral oil fractions of medium tohigh boiling point, such as kerosene, or diesel oil, furthermore coaltar oils and oils of vegetable or animal origin, aliphatic, cyclic andaromatic hydrocarbons, e.g. paraffin, tetrahydronaphthalene, alkylatednaphthalenes or their derivatives, alkylated benzenes or theirderivatives, alcohols such as methanol, ethanol, propanol, butanol,cyclohexanol, ketones such as cyclohexanone or strongly polar solvents,e.g. amines, such as N-methylpyrrolidone or water.

Aqueous application forms can be prepared from emulsion concentrations,suspensions, pastes, wettable powders or water-dispersible granules byaddition of water. For the preparation of emulsions, pastes or oildispersions, the saccharin-5-carbonyl derivatives can be homogenized inwater, as such or dissolved in an oil or solvent, by means of wettingagents, adherents, dispersants or emulsifiers. However, concentratesconsisting of active substance, wetting agent, adherent, dispersant oremulsifier and possibly solvent or oil can also be prepared, which aresuitable for dilution with water.

Suitable surface-active substances are the alkali metal, alkaline earthmetal and ammonium salts of aromatic sulfonic acids, e.g. ligno-,phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and also offatty acids, alkyl and alkylaryl sulfonates, alkyl, lauryl ether andfatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- andoctadecanols, and also of fatty alcohol glycol ethers, condensationproducts of sulfonated naphthalene and its derivatives withformaldehyde, condensation products of naphthalene or of thenaphthalenesulfonic acids with phenol and formaldehyde, polyoxyethyleneoctylphenyl ethers, ethoxylated isooctyl, octyl- or nonylphenyl,alkylphenyl or tributylphenyl polyglycol ethers, alkylaryl polyetheralcohols, isotridecyl alcohol, fatty alcohol-ethylene oxide condensates,ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylenealkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters,lignin-sulfite waste liquors or methylcellulose.

Powder compositions, broadcasting compositions and dusting compositionscan be prepared by mixing or joint grinding of the active substanceswith a solid carrier.

Granules, e.g. coated, impregnated and homogeneous granules, can beprepared by binding the active compounds to solid carriers. Solidcarriers are mineral earths such as silicic acids, silica gels,silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay,dolomite, diatomaceous earth, calcium sulfate and magnesium sulfate,magnesium oxide, ground synthetic materials, fertilizers, such asammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and plantproducts such as cereal flour, tree bark meal, wood meal and nutshellmeal, cellulose powder or other solid carriers.

The concentrations of the active compounds I in the ready-to-usepreparations can be varied within wide ranges. The formulations ingeneral contain 0.001 to 98% by weight, preferably 0.01 to 95% byweight, of at least one active compound. The active compounds areemployed here in a purity of 90% to 100%, preferably 95% to 100%(according to NMR spectrum).

The compounds I according to the invention can be formulated, forexample, as follows:

I 20 parts by weight of a compound of the formula I are dissolved in amixture which consists of 80 parts by weight of alkylated benzene, 10parts by weight of the addition product of 8 to 10 mol of ethylene oxideto 1 mol of oleic acid N-monoethanolamide, 5 parts by weight of calciumsalt of dodecylbenzenesulfonic acid and 5 parts by weight of theaddition product of 40 mol of ethylene oxide to 1 mol of castor oil. Bypouring out and finely dispersing the solution in 100,000 parts byweight of water, an aqueous dispersion is obtained which contains 0.02%by weight of the active compound.

II 20 parts by weight of a compound of the formula I are dissolved in amixture which consists of 40 parts by weight of cyclohexanone, 30 partsby weight of isobutanol, 20 parts by weight of the addition product of 7mol of ethylene oxide to 1 mol of isooctylphenol and 10 parts by weightof the addition product of 40 mol of ethylene oxide to 1 mol of castoroil. By pouring the solution into and finely dispersing it in 100,000parts by weight of water, an aqueous dispersion is obtained whichcontains 0.02% by weight of the active compound.

III 20 parts by weight of a compound of the formula I are dissolved in amixture which consists of 25 parts by weight of cyclohexanone, 65 partsby weight of a mineral oil fraction of boiling point 210 to 280° C. and10 parts by weight of the addition product of 40 mol of ethylene oxideto 1 mol of castor oil. By pouring the solution into and finelydispersing it in 100,000 parts by weight of water, an aqueous dispersionis obtained which contains 0.02% by weight of the active compound.

IV 20 parts by weight of a compound of the formula I are well mixed with3 parts by weight of the sodium salt of diisobutylnaphthalenesulfonicacid, 17 parts by weight of the sodium salt of a lignosulfonic acid froma sulfite waste liquor and 60 parts by weight of powdered silica gel andground in a hammer mill. By finely dispersing the mixture in 20,000parts by weight of water, a spray mixture is obtained which contains0.1% by weight of the active compound.

V 3 parts by weight of a compound of the formula I are mixed with 97parts by weight of finely divided kaolin. In this way, a dusting agentis obtained which contains 3% by weight of the active compound.

VI 20 parts by weight of a compound of the formula I are intimatelymixed with 2 parts by weight of calcium salt of dodecylbenzenesulfonicacid, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts byweight of sodium salt of a phenol/urea/formaldehyde condensate and 68parts by weight of a paraffinic mineral oil. A stable oily dispersion isobtained.

VII 1 part by weight of a compound of the formula I is dissolved in amixture which consists of 70 parts by weight of cyclohexanone, 20 paresby weight of ethoxylated isooctylphenol and 10 parts by weight ofethoxylated castor oil. A stable emulsion concentrate is obtained.

VIII 1 part by weight of a compound of the formula I is dissolved in amixture which consists of 80 parts by weight of cyclohexanone and 20parts by weight of Wettol ® EM 31 (nonionic emulsifier based onethoxylated castor oil). A stable emulsion concentrate is obtained.

To broaden the spectrum of action and to achieve synergistic effects,the saccharin-5-carbonyl derivatives of the formula I or the cropprotection compositions comprising this compound can be combined withnumerous representatives of other herbicidal or growth-regulating groupsof active compounds and applied together or separately. For example,suitable mixture components are 1,2,4-thiadiazoles, 1,3,4-thiadiazoles,amides, aminophosphoric acid and its derivatives, aminotriazoles,anilides, (het)aryloxyalkanoic acid and its derivatives, benzoic acidand its derivatives, benzothiadiazinones, 2-aroyl-1,3-cyclohexanediones,hetaryl aryl ketones, benzylisoxazolidinones, meta-CF₃-phenylderivatives, carbamates, quinolinecarboxylic acid and its derivatives,chloroacetanilides, cyclohexane-1,3-dione derivatives, diazines,dichloropropionic acid and its derivatives, dihydrobenzofurans,dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers,dipyridyls, halocarboxylic acids and their derivatives, ureas,3-phenyluracils, imidazoles, imidazolinones,N-phenyl-3,4,5,6-tetrahydrophthalimides, oxadiazoles, oxiranes, phenols,aryloxy- or heteroaryloxyphenoxypropionic acid esters, phenylacetic acidand its derivatives, phenylpropionic acid and its derivatives,pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acid and itsderivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines,triazinones, triazolinones, triazolecarboxamides and uracils.

Moreover, it may be of benefit to apply the compounds I on their own orin combination with other herbicides and/or mixed with further cropprotection agents, for example with agents for controlling pests orphytopathogenic fungi or bacteria, the compounds being applied jointlyor separately with these. Furthermore of interest is the miscibilitywith mineral salt solutions, which are employed for the elimination ofnutritional and trace element deficiencies. Nonphytotoxic oils and oilconcentrates can also be added.

Depending on the control target, time of year, target plants and stageof growth, the application rates of active compound are 0.001 to 3.0,preferably 0.01 to 1.0, kg/ha of active substance (a.s.).

EXAMPLE 1

Active compound from bicyclo[3.2.]oct-3-en-2-one and2,4-dimethylsaccharin-5-carbonyl chloride (No. 1.1 in Table 1)

3.03 g (0.22 mol) of bicyclo[3.2.1]oct-3-en-2-one and 6.10 g (0.022 mol)of 2,4-dimethylsaccharin-5-carbonyl chloride are suspended in 100 ml ofmethylene chloride and 2.43 g (0.024 mol) of triethylamine are added.The mixture is additionally stirred at 25° C. for 2 hours, concentratedand the residue is chromatographed on silica gel (methylenechloride/ethyl acetate 8:2). The enol ester is then dissolved in 300 mlof acetonitrile and treated with 4.80 g (0.047 mol) of triethylamine and0.3 g (0.003 mol) of trimethylsilyl cyanide. It is stirred at 25° C.overnight, concentrated, the residue is taken up with ethyl acetate, andthe mixture is washed with dilute hydrochloric acid, dried andconcentrated again. The residue is digested with methanol and filteredoff with suction. 6.0 g (73% yield) of a white solid having a meltingpoint of>220° C. are obtained

In the same manner, the following compounds in Table 1 can be obtained:

TABLE 1 I.A

Current No. M Z ν 1.1.  H CH₃ IR: ν [cm⁻¹]: 1724, 1676 1.2.  H C₂H₅ IR:ν [cm⁻¹]: 1728, 1672 1.3.  H n-C₃H₇ 1.4.  H i-C₃H₇ 1.5.  H n-C₄H₉ 1.6. H i-C₄H₉ 1.7.  H s-C₄H₉ 1.8.  H t-C₄H₉ 1.9.  H cyclopropyl 1.10. Hcyclobutyl 1.11. H cyclopentyl 1.12. H cyclohexyl 1.13. H allyl 1.14. Hpropargyl 1.15. H benzyl 1.16. H phenyl 1.17. H 4-Cl-phenyl 1.18. H2,4-dichlorophenyl 1.19. H 4-methylphenyl 1.20. H 4-methoxyphenyl 1.21.CH₃ CH₃ 1.22. CH₃ C₂H₅ 1.23. CH₃ n-C₃H₇ 1.24. CH₃ i-C₃H₇ 1.25. CH₃n-C₄H₉ 1.26. CH₃ i-C₄H₉ 1.27. CH₃ s-C₄H₉ 1.28. CH₃ t-C₄H₉ 1.29. CH₃cyclopropyl 1.30. CH₃ cyclobutyl 1.31. CH₃ cyclopentyl 1.32. CH₃cyclohexyl 1.33. CH₃ allyl 1.34. CH₃ propargyl 1.35. CH₃ benzyl 1.36.CH₃ phenyl 1.37. CH₃ 4-Cl-phenyl 1.38. CH₃ 2,4-dichlorophenyl 1.39. CH₃4-methylphenyl 1.40. CH₃ 4-methoxyphenyl 1.41. Cl CH₃ 1.42. Cl C₂H₅1.43. Cl n-C₃H₇ 1.44. Cl i-C₃H₇ 1.45. Cl n-C₄H₉ 1.46. Cl i-C₄H₉ 1.47. Cls-C₄H₉ 1.48. Cl t-C₄H₉ 1.49. Cl cyclopropyl 1.50. Cl cyclobutyl 1.51. Clcyclopentyl 1.52. Cl cyclohexyl 1.53. Cl allyl 1.54. Cl propargyl 1.55.Cl benzyl 1.56. Cl phenyl 1.57. Cl 4-Cl-phenyl 1.58. Cl2,4-dichlorophenyl 1.59. Cl 4-methylphenyl 1.60. Cl 4-methoxyphenyl1.61. H CH₃ Na salt; IR: ν [cm⁻¹]: 1730, 1647 1.62. H CH₃ K salt; IR: ν[cm⁻¹]: 1728, 1645 1.63. H CH₃ Mg salt 1.64. H CH₃ Ca salt 1.65. H CH₃Li salt; IR: ν [cm⁻¹]: 1730, 1647 1.66. H CH₃ Zn salt 1.67. H CH₃ NH₄salt 1.68. H CH₃ NHEt₂ salt 1.69. H CH₃ NEt₃ salt 1.70. H CH₃ H₂N-iPrsalt

In the same manner, the following compounds I. B. in Table 2 can beobtained, where M and Z have the meanings indicated in Table 1:

In the same manner, the following compounds I.C. in Table 3 can beobtained, where M and Z have the meanings indicated in Table 1:

EXAMPLE 2

It was possible to show the herbicidal action of thesaccharin-5-carbonyl derivatives of the formula I by means of greenhousetests:

The cultivation containers used were plastic pots containing loamy sandwith approximately 3.0% humus as a substrate. The seeds of the testplants were sown separately according to species.

In the case of preemergence treatment, the active compounds suspended oremulsified in water were applied directly after sowing by means offinely dispersing nozzles. The containers were lightly watered in orderto promote germination and growth, and then covered with transparentplastic hoods until the plants had taken root. This covering causesuniform germination of the test plants if this is not adversely affectedby the active compounds. The application rate for preemergence treatmentwas 0.125 or 0.0625 kg/ha of a.s.

For the purpose of postemergence treatment, the test plants were eachfirst raised to a growth height of 3 to 15 cm, according to growth form,and then treated with the active compounds suspended or emulsified inwater. For this, the test plants were either sown directly and grown inthe same containers or they were first raised separately as seed plantsand transplanted into the test containers a few days before thetreatment.

The plants were kept species-specifically at temperatures of 10-25° C.or 20-35° C. The test period extended over 2 to 4 weeks. During thistime, the plants were tended, and their reaction to the individualtreatments was assessed.

Assessment was carried out on a scale from 0 to 100. In this case, 100means no emergence of the plants or complete destruction at least of theabove-ground parts and 0 means no damage or a normal course of growth.

The plants used in the greenhouse tests were made up of the followingspecies:

Botanical name Common name Glycine max soybean (GLXMA) Chenopodium albumlambsquarter (CHEAL) digitaria sanguinalis crabgrass, large (DIGSA)Echinochloa crus galli barnyard grass, (ECHCG) common Setaria viridisfoxtail, green (SETVI)

Preemergence, weed grasses and broad-leaved plants are very wellcontrolled using the compound 1.1 at 0.125 and 0.0625 kg/ha a.s.

Table 1: Selective activity when used preemergence in the greenhouse

Compound according to Example No. 1.1.

Application rates Application rates (kg/ha of a.s.) (kg/ha of a.s.) Testplants 0.125 0.0625 GLXMA 0 0 CHEAL 98 98 DIGSA 98 98 ECHCG 98 98 SETVI100 98 a.s. = active substance

We claim:
 1. A saccharin-5-carbonyl derivative of the formula I

in which the substituents have the following meanings: L is C₁-C₅-alkyl,C₁-C₆-alkoxy; Z is C₁-C₆-alkyl, C₃-C₈-cycloalkyl, C₃-C₆-alkenyl,C₃-C₅-alkynyl, phenyl-C₁-C₆-alkyl or phenyl, where the phenyl rings canbe mono- or polysubstituted by C₁-C₆-alkyl, C₁-C₆-alkoxy or halogen; Mis hydrogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, halogen, cyano, nitro orhalo-C₁-C₆-alkyl; R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ are hydrogen orC₁-C₆-alkyl; or the agriculturally utilizable salts of the compound I.2. A saccharin derivative of the formula I as claimed in claim 1, inwhich L is methyl, ethyl, methoxy or ethoxy.
 3. A saccharin derivativeof the formula I as claimed in claim 1, in which Z is C₁-C₄-alkyl,C₃-C₈-cycloalkyl, C₃-C₆-alkenyl, C₃-C₅-alkynyl, phenyl or benzyl.
 4. Asaccharin derivative of the formula I as claimed in claim 1, in which Zis methyl, ethyl, i-propyl, i-butyl, t-butyl, cyclopropyl, cyclohexyl,allyl, propargyl, phenyl or benzyl.
 5. A saccharin derivative of theformula I as claimed in claim 1, in which M is hydrogen, methyl, ethyl,methoxy, ethoxy, fluoro, chloro, cyano, nitro or trifluoromethyl.
 6. Asaccharin derivative of the formula I as claimed in claim 1, in which Mis hydrogen, methyl, ethyl, methoxy or chloro.
 7. A saccharin derivativeof the formula I as claimed in claim 1, in which R¹ to R⁸ are hydrogen.8. A saccharin derivative of the formula I as claimed in claim 1, inwhich one, two or three of the radicals R¹ to R⁸ is/are methyl, ethyl,n-propyl or n-butyl, and the remaining radicals are hydrogen.
 9. Asaccharin derivative of the formula I as claimed in claim 1, where R⁷and R⁸ are identical and are hydrogen or methyl.
 10. A saccharinderivative of the formula I as claimed in claim 1, where R⁶ is hydrogenor methyl.
 11. A crop protection composition comprising at least onesaccharin derivative of the formula I as claimed in claim 1 andcustomary inert additives.
 12. A crop protection composition as claimedin claim 11 having herbicidal or growth-regulating action.
 13. A processfor the treatment of plants for controlling undesired growth of harmfulplants, which comprises bringing the plants or their habitat intocontact with an effective amount of a compound of the formula I asclaimed in claim 1 or a composition comprising this compound.
 14. Aprocess for controlling undesired vegetation, which comprises allowing aherbicidally effective amount of a compound of the formula I accordingto claim 1 to act on the plants or their habitat.
 15. A process forpreparing crop protection compositions as claimed in claim 11, whichcomprises mixing at least one compound of the formula I with inertadditives and processing the mixture into suitable application forms ascrop protection compositions.